Production of titanium tetrachloride



Patented Apr. 2, 1929.

UNITED STATES PATENT OFFICE.

DI BOHDEN, OI BALTIIOBE, MARYLAND, ASSIGNOR 'I'O COMMERCIAL PIG- mas CORPORATION, 01' NEW YORK, N. Y., A CORPORATION 91! DELAWARE.

PRODUCTION OF TITANIUM TETEACHLORIDE Io Drawin 3.

My invention pertains to the production of titanium tetrachloride and relates more specifically to an improvement in the procass of producing this substance by treatlng a 5 mixture of titanic material and carbon with chlorine at an elevated temperature. Over one hundred years ago, J. B. A. Dumas discovered that titanium tetrachloride could be pre ared by submitting a mixture of titanic oxi e and carbon maintained at red heat to the action of chlorine. Since the work of l Dumas, various later workers have suggested modifications by means of which the process has-been improved and the yields of material obtained have been increased. Nevertheless, past attempts to operate the recess on an economical basis have failed, or while very ood results have been obtained in the aboratory, the transfer of the process to a large industrial scale has been prevented by difliculties of operation which the present invention is designed to overcome.

lUne of the principal difliculties en countered in attempts to o erate the process on an industrial scale has am the difficulty of securing a correct admixture of titanic material and carbon. The literature has shown that a suitable mixture for laboratory use may be prepared from powdered TiO and lampblack. However, such a fine, dusty material is unsuited for industrial treatmeal, and the practical diliiculties in chlorinating this material in a large appara tus at any reasonable rate of speed have been thus far insuperable. The treatment of a mixture of lumps of carbon and TiO can be carried out on a large scale in simple up paratus with relativeease, since the chlorine will penetrate easily between the lumps, but in such a process the rate of reaction 1s very low, the chlorine is inefiiciently used, and the process is hence uite expensive.

in his U. S. atent 1,179,394. Barton has proposed still a different method of securing opermixture of titanic material and can that can be efficiently chlorinated. He res a powdered titaniferous material such lltl till

in "the absence of air he produces a is cinder. This cinder, owing to its tough, granular structure and its inerh'nixture of titaniierous material orn may be easily chlorinated.

"pr m-ed process for producing titan 'ture with carbon.

stile with a coking coal and by heat treat- Application filed February 8, 1928. Serial No. 252,946.

nium tetrachloride relates in part to; a simpler and more economical methoctef producing the requisite intimate admixture of titanic material and carbon in the form of a tough,

chlorinating tower. Briefly, this aspect of my invention relates to the use of titanic material itself as a binder in therequisite mix- By means of my invention a suitable mass for treatment may be prepared by the simple admixture of the substances with an aqueous solution, and the subsequent evaporation of the water therefrom, whereby a mass suitable for treatment is produced in the simplest possible fashion, without the necessity of high temperature treatment, elaborate apparatus or the like.

Another obect of my invention is to provide a means or the production of ure titanium tetrachloride uncontaminate by iron. This may be accomplished by the use of industrially pure titanium dioxide as a source of raw material. On the other hand, my process is equally adaptable to the treatment of other less pure titaniferous materials such as rutile or ilnienite.

In preparing a suitable granular, porous, non-crumbling mass containing titamferous material and carbon, I make use of the peculiar colloidal properties of titanium dioxide. By a. suitable process hereinafter described, it is possible to peptize relatively pure recipitated lIiO to form an a ueous colloidal suspension (peptized solutioril containing as much as 550 grams-of TiO per liter. Such a solution is as fluid as water, is un filtrable, and behaves as a binder or mineral glue. When particles of solid substances. Slltl'l for example as carbon and ore, are mixed with this peptiaed solution and the entire mixture dried, it tough, granular mass results. After being" broken into fragmanta it is quite suitable for treatment with chlorine at an elevated temperature to pro doc-e titanium tetrachloride.

For the production of titanium tetrachloride for ordinary industrial purposes, granular masses prepared bymixing carbon and titanium ore cemented together with about 20% (dry weight) of peptized TiO are suitable for chlorination. Such a mass may be conveniently prepared by mixing 20-25 parts of finely ground carbon such as coke or charcoal with 60-50 parts of iuwdered ore, after which 20 parts (dry weight) of TiO, in the form of a peptizedsolution is added to serve as a binder. pure titanium tetrachloride the titanium ore may be wholly replaced by pure TiO For example, 20-25 parts of carbon ma be mixed with 80-75 parts of colloidal T10 in the form of a peptized solution or alternatively, part of the tized TiO. may be replaced by coaigulated precipitated) T10 any event, the moist mass thus obtained may be spread out on a suitable surface and allowed to drafter which it may be broken up into suitalile fra ments for the chlorination treatment. A ternatively, the moist mass may be put through a briquetting machine to roduce suitable small pellets of material, which may then be dried.

The eptized solution used as a binder may be easi y prepared from ordinary titaniumdioxide precipitated by hydrolysis of the sulfate solution in the wel -known manner.

Prior to peptization, the 'lliO must first be treated to remove adsorbed sulfuric acid, since the presence of olybasic acid prevents peptization. The so furic acid may be removed by washing the precipitate with an alkaline solution such as a ua-ammonia or sodium carbonate solution. he peptized solution may then be pre ared from the washed TiO precipitate as to lows:

To 1 kilogram of TiO in the form of a wet filter-cake containing about 60% of water, there is added 150 ams of concentrated hydrochloric acid, w ich substance,v is incorporated with the cake by ordinary mixing rocesses. The mass becomes completely aid as soon as the hydrochloric acid is added since the latter material converts the TiO to the colloidal form, producing a peptized solution. It is not necessary to use concen trated hydrochloric acid for this purpose, and in its place an equivalent uantity of dilute acid may be employed. 11 any event, the acid is diluted as soon as peptization occurs, on account of the presence of a large amount of water in the filter-cake. In place of hydrochloric acid, another monobasic acid such as nitric acid or hydrobromic acid may be used.

Instead of first removing the adsorbed sulfuric acid from the filter-cake, and then peptizing the latter with hydrochloric acid, I

may prefer to combine these two processes. For example. I may take the filer-cake containing adsorbed sulfulric acid and mix with it sufficient barium chloride to react with all of the sulfuric acid to produce insoluble barium sulfate. The hydrochloric acid generated as a by-product of this reaction will If it is'desired to produce.

cause the peptizatiou of the TiO,. In place of barium chloride, I may use any other chloride salt, the metallic element of which forms an insoluble sulfate.

To produce titanium tetrachloride, I then subject the granular masses or briquettes previously mentioned to the action of chlorine gas at an elevated temperature. The chlorination may be conveniently conducted by placing the granular mass in an ordinary quartz tube, to which heat may be applied. There is no critical temperature for chlorination and good results are obtained so long,' as the mass is held within a temperature range of 650 to 800 C. If the material treated comprises only dried pe tized TiO and finely round carbon. the c ilorination may he satlsfactorily conducted at a temperature as low as 500 C The rate at which the chlorine gas is added will, of course, depend entirely 86 on the cross-sectional area of the chlorination apparatus. The gases evolved from the chlorination apparatus are cooled and titanium tetrachloride is thus recovered as a liquid. The residual chlorine gas may be recovered and used in the process.

The puritv of the titanium tetrachloride produced will depend entirely on the nature of the titaniferous material used. If pure titanium dioxide is used, the tetrachloride produced will be quite ure. If rutile or ilmcnite are used, some erric chloride will also be produced and will be condensed with the titanium tetrachloride.

ever, and for that reason it is advantageous to conduct the chlorination reaction at the lowest possible temperature. By doing this, one is able to produce a first fraction of practically pure titanium chloride, and all of the iron chloride produced as an impurity will be found in the latter part of the titanium The latter substance forms at a lower temperature, howtctrachloride produced by the reaction.

It is not necessary to continue the chlorination until all of the raw material is consumed and. in fact, that is impracticable since the granular structure of the mass would be destroycd and the chlorination process would be rendered diflicult toward the end. The residual mass left after chlorination may be incorporated with fresh carbon, titaniferous material and peptized solution and used over again. In the case of very crude titaniferous materials, however, such as ores that contain large quantities of silica and other im uritics, it is sometimes preferable to discar the chlorination residue rather than to incorporate it in a new mixture.

Titanium tetrachloride when pure, is a transparent. colorless liquid boiling at about 137 C. It solidifies at 23 C. The purity of the product obtained by my process depends on the purity of the titaniferous matorial used. It may be purified from residual chlorine by refluxing in an atmosphere of nitrogen. Ferric chloride me be removed b fractional distillation and the fraction boi ing at 136- 1 G. may be further purified by shaking with mercury and sodium amalgam.

Now, having described my invention, I claim:

1. A process for the production of titanium tetrachloride which comprises mixing to gether carbon, at tita-niferous substance, and a colloidal suspension of titanium dioxide, drying said mixture to produce a tough mass, and subjecting fragments of said mass to the action of chlorine.

2. A recess for the production of titanium tetrach oricle which com rises mixing toigether carbon, titanium ioxide, and a co1- oidel suspension of titanium dioxide, dryin acid mixture to produce a tough mass, on

subjecting fragments of said mass to the so tion of chlorine.

3., A process for the production oi? tituni urn tetrachloride which comprises mining to gcther carbon and a colloidal suspension oi titanium dioxide, drying said mixture to produce a tough mess, and subjecting fragments of said mess to the action of chlorine.

4. As a new com osition of matter. o min.- ture of carbon an a titaniferous substonce cemented together by dry peptized TiU 5. As a new composition of matter, a, min

ture of carbon and titanium dioxide cemented together by dry peptized TiO 6. As a new composition of matter, a tough mess comprising carbon and dry peptisedi CHARLES or. RQHDEN. 

